2905-57-9

Upstream product

• 2568-57-2 N-(3-phenyl-2-propynyl)piperidine 
• 3339-05-7 1-(3-chloro-3-phenylpropyl)piperidine hydrochloride 
• 110-89-4 piperidine 
• 153706-94-6 3-Phenethyl-[1,2,4]trioxolane 
• 768-56-9 4-Phenylbut-1-ene 
• 60-29-7 diethyl ether 
• 93516-09-7 3-phenyl-1,3-dipiperidino-propene 
• 64-17-5 ethanol 
• 110-82-7 cyclohexane 
• 100-42-5 styrene 
• 201230-82-2 carbon monoxide 
• 21924-11-8 1-(3-phenylpropanoyl)piperidine 
• 645-45-4 hydrocinnamic acid chloride 
• 14371-10-9 (E)-3-phenylpropenal 

Relevant academic research and scientific papers

Zirconium-hydride-catalyzed site-selective hydroboration of amides for the synthesis of amines: Mechanism, scope, and application

Developing mild and efficient catalytic methods for the selective synthesis of amines is a longstanding research objective. In this respect, catalytic deoxygenative amide reduction has proven to be promising but challenging, as this approach necessitates selective C–O bond cleavage. Herein, we report the selective hydroboration of primary, secondary, and tertiary amides at room temperature catalyzed by an earth-abundant-metal catalyst, Zr-H, for accessing diverse amines. Various readily reducible functional groups, such as esters, alkynes, and alkenes, were well tolerated. Furthermore, the methodology was extended to the synthesis of bio- and drug-derived amines. Detailed mechanistic studies revealed a reaction pathway entailing aldehyde and amido complex formation via an unusual C–N bond cleavage-reformation process, followed by C–O bond cleavage.

Method used for reduction of tertiary amide into alcohols and/or amines

The invention discloses a method used for reduction of tertiary amide into alcohols and/or amines. The method comprises following steps: tertiary amide, an alkali metal reagent, and a proton donor agent are added into an organic solvent for a following reaction selectively: when the proton donor agent is a raw material alcohol and/or inorganic salt aqueous solution, the reaction product is an alcohol compound and/or tertiary amine compound. The method is capable of realizing selective reduction of tertiary amide into alcohols and tertiary amine compounds, the yield is high, the suitable rangeis wide, operation is safe and simple, the adopted raw materials are cheap and easily available; no precious metal catalyst, toxic silanes, and flammable and combustible metal hydrides are adopted; notoxic by product is generated; reaction is more friendly to the environment; problems in the prior art that amide compound reducing method operation is complex, conditions are strict, and control ofproducts is difficult are solved.

Reduction and Reductive Deuteration of Tertiary Amides Mediated by Sodium Dispersions with Distinct Proton Donor-Dependent Chemoselectivity

A practical and scalable single electron transfer reduction mediated by sodium dispersions has been developed for the reduction and reductive deuteration of tertiary amides. The chemoselectivity of this method highly depends on the nature of the proton donor. The challenging reduction via C-N bond cleavage has been achieved using Na/EtOH, affording alcohol products, while the use of Na/NaOH/H2O leads to the formation of amines via selective C-O scission. Sodium dispersions with high specific surface areas are crucial to obtain high yields and good chemoselectivity. This new method tolerates a range of tertiary amides. Moreover, the corresponding reductive deuterations mediated by Na/EtOD-d1 and Na/NaOH/D2O afford useful α,α-dideuterio alcohols and α,α-dideuterio amines with an excellent deuterium content.

Iron-Catalyzed Reductive Amination of Aldehydes in Isopropyl Alcohol/Water Media as Hydrogen Sources

Reductive amination can be carried in i-PrOH/H2O as hydrogen sources using commercially available iron carbonyl complexes. Within an aqueous alkaline environment, a hydridocarboferrate is formed and its reducing potential is exploited for hydrogenation of the imine (or iminium ion) obtained in situ from aldehydes or ketones, and primary or secondary amines in almost equimolar ratio. This completely sustainable and hydrogen-free process proceeds at 100 °C using Fe3(CO)12 as catalyst precursor under convectional heating while Fe2(CO)9 gave better results when the reaction was carried out under MW dielectric heating. Both enolizable and non-enolizable aldehydes may be successfully employed in reactions with aliphatic and aromatic amines. (Figure presented.).

Nickel-Catalyzed Reduction of Secondary and Tertiary Amides

The nickel-catalyzed reduction of secondary and tertiary amides to give amine products is reported. The transformation is tolerant of extensive variation with respect to the amide substrate, proceeds in the presence of esters and epimerizable stereocenters, and can be used to achieve the reduction of lactams. Moreover, this methodology provides a simple tactic for accessing medicinally relevant α-deuterated amines.

Mild Hydrogenation of Amides to Amines over a Platinum-Vanadium Bimetallic Catalyst

Hydrogenation of amides to amines is an important reaction, but the need for high temperatures and H2 pressures is a problem. Catalysts that are effective under mild reaction conditions, that is, lower than 30 bar H2 and 70 °C, have not yet been reported. Here, the mild hydrogenation of amides was achieved for the first time by using a Pt-V bimetallic catalyst. Amide hydrogenation, at either 1 bar H2 at 70 °C or 5 bar H2 at room temperature was achieved using the bimetallic catalyst. The mild reaction conditions enable highly selective hydrogenation of various amides to the corresponding amines, while inhibiting arene hydrogenation. Catalyst characterization showed that the origin of the catalytic activity for the bimetallic catalyst is the oxophilic V-decorated Pt nanoparticles, which are 2 nm in diameter.

Scandium-catalysed intermolecular hydroaminoalkylation of olefins with aliphatic tertiary amines

A homoleptic scandium trialkyl complex in combination with a borate compound served as an excellent catalyst for the C-H addition of aliphatic tertiary amines to olefins. This highly regiospecific, 100% atom efficient C-H bond alkylation reaction was applicable to a wide variety of tertiary amines and olefins, including functionalised styrenes and unactivated α-olefins. This work represents the first example of rare-earth catalysed olefin hydroaminoalkylation and also the first example of catalytic C-H addition of aliphatic tertiary amines to olefins with any catalyst.

Copper-catalyzed oxygen atom transfer of N-oxides leading to a facile deoxygenation procedure applicable to both heterocyclic and amine N-oxides

Deoxygenation of various types of N-oxides including both heterocyclic and alkyl(aryl)amine derivatives has successfully been developed by the copper-catalyzed oxygen atom transfer using diazo compounds as the oxygen acceptor. The reaction proceeds smoothly over a broad range of substrates with excellent functional group tolerance under mild conditions. This journal is

Hydroaminomethylation of styrene catalyzed by rhodium complexes containing chiral diphosphine ligands and mechanistic studies: Why is there a lack of asymmetric induction?

Various chiral diphosphine ligands (P-P) have been introduced in the coordination sphere of neutral or cationic rhodium complexes, and the generated species catalyze efficiently the hydroaminomethylation reaction of styrene with piperidine. The diphospholane ligand family is particularly adapted to this tandem reaction leading to the branched amine with good chemo- and regioselectivity. We analyzed in detail the main reasons why the reaction proceeds with no enantioselectivity. Catalytic and HP-NMR experiments reveal the presence of the [Rh(H)(CO)2(P-P)] species as the resting state. DFT calculations allow us to elucidate the mechanism of the hydrogenation of the branched (Z) or (E)-enamine. From the [Rh(H)(CO)(P-P)] active species, the coordination of the two enamine isomers, the hydride transfer, the H2 activation, and then the final reductive elimination follow similar energetic pathways, explaining the lack of enantioselectivity for the present substrates. Analysis of the energy-demanding steps highlights the formation of the active species as crucial for this rate-limiting hydrogenation reaction.

Phosphine- and hydrogen-free: Highly regioselective ruthenium-catalyzed hydroaminomethylation of olefins

A highly regioselective ruthenium-catalyzed hydroaminomethylation of olefins is reported. Using easily available trirutheniumdodecacarbonyl an efficient sequence consisting of a water-gas shift reaction, hydroformylation of olefins, with subsequent imine or enamine formation and final reduction is realized. This novel procedure is highly practical (ligand-free, one pot) and economic (low catalyst loading and inexpensive metal). Bulk industrial as well as functionalized olefins react with various amines to give the corresponding tertiary amines generally in high yields (up to 92), excellent regioselectivities (n/iso>99:1), and full chemoselectivity in favor of terminal olefins.